US4146519A - Air-drying acrylate lacquer binders - Google Patents

Air-drying acrylate lacquer binders Download PDF

Info

Publication number
US4146519A
US4146519A US05/876,539 US87653978A US4146519A US 4146519 A US4146519 A US 4146519A US 87653978 A US87653978 A US 87653978A US 4146519 A US4146519 A US 4146519A
Authority
US
United States
Prior art keywords
weight
acid
drying
copolymer
acid anhydride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/876,539
Other languages
English (en)
Inventor
Rolf Dhein
Lothar Fleiter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Application granted granted Critical
Publication of US4146519A publication Critical patent/US4146519A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups

Definitions

  • This invention relates to air-drying lacquer binders obtained from copolymers of styrene, (meth)acrylates and glycidyl (meth acrylates which are esterified to acid numbers of from 0 to 10 with from 22 to 50% of drying fatty acid mixtures after the copolymerisation process and are then reacted with dicarboxylic acid anhydrides (from 0.5 to 3%) until acid numbers of from 5 to 15 are reached.
  • lacquer binders have excellent drying properties even after the addition of anti-skinning agents and their capacity to absorb and to wet pigments is excellent. Other advantages will appear from the description.
  • copolymers of styrene and glycidyl methacrylate can be reacted with drying fatty acids so that the carboxyl groups of the fatty acid are added to the epoxide groups of the copolymer, and then the resulting reaction products, which have acid numbers of about 1.2 to 5, based on the solid substance, can be used as air-drying lacquer binders (see British Pat. No. 767,476).
  • copolymers of glycidyl (meth)acrylate and vinyl monomers or vinylidene monomers can be reacted with drying fatty acids and used as air-drying lacquer binders (with acid numbers of 10 to 15).
  • Vinyl and vinylidene monomers are intended to mean vinyl toluene, (meth)acrylonitrile and (meth) acrylic acid esters (see British Pat. No. 793,776).
  • copolymers are prepared from at least one vinyl monomer and at least one comonomer which contains epoxide groups, the copolymers are esterified with drying fatty acids to produce products with acid numbers of between about 12 and 16, based on the solid substance, and the hydroxyl groups formed in the esterification reaction are reacted with a dicarboxylic acid anhydride to from semiester groups, acid numbers of between about 20 and about 60, based on the quantity of binder, being necessary to produce a sufficiently pronounced effect.
  • Binders which have been modified in this way have very good pigment absorption and wetting properties, presumably due to their high acid numbers, and they rapidly dry completely, have relatively constant drying times and good processing properties for lacquers, and give rise to films with high elasticity and hardness. Like many air-drying lacquers, however, the lacquers obtained from these binders have the undesirable characteristic of thickening and forming a skin when stored so that they require the addition of an anti-skinning agent.
  • An object of the present invention is to modify the air-drying binders of German Offenlegungsschrift No. 1,720,697 so that in addition to their excellent pigment absorption and wetting capacity they would also have very satisfactory processing properties for lacquer technology, great hardness, high elasticity and high gloss in the dried films, as well as short drying times even after the addition of an anti-skinning agent.
  • German Offenlegungsschrift No. 1,720,697 which have been esterified with air-drying fatty acids up to acid numbers of from 0 to 10 and then reacted with a dicarboxylic acid anhydride, preferably tetrahydrophthalic acid anhydride or its isomers, to a total acid number of from 5 to 15. It is preferred to use the special copolymers selected from German Offenlegungsschrift No. 1,720,697. In principle, it is suitable to use copolymers of glycidyl (meth)acrylate with at least one vinyl monomer, particularly with the vinyl monomers indicated in German Offenlegungsschrift No. 1,720,697.
  • the binders according to the invention are distinguished not only by their very good processing properties for lacquer technology and by the good properties of the films obtained after drying but also by their very good pigment absorption and wetting properties, as well as the short drying times obtained even after the addition of an anti-skinning agent. This result is surprising since in view of the teaching according to German Offenlegungsschrift No. 1,720,697 it was not foreseeable that after reduction of the acid numbers from 20-60 to 5-15 it would be possible not only to obtain short drying times after the addition of an anti-skinning agent but also to preserve the very good pigment absorption and wetting characteristics of the binders.
  • the present invention thus provides air-drying lacquer binders of copolymers obtained from copolymerised units of
  • copolymers have been esterified to an acid number of from 0 to 10 with from 22 to 50% by weight of air-drying fatty acids, based on the copolymer and the drying fatty acids and dicarboxylic acid anhydride, and the hydroxyl groups formed in the reaction have subsequently been reacted with from 0.5 to 3% by weight of dicarboxylic acid anhydride, based on the quantity of copolymer and drying fatty acids and dicarboxylic acid anhydride, characterised in that the binders have final acid numbers of from 5 to 15, this final acid number being made up of the acid number of from 0 to 10 obtained by the esterification with the drying fatty acid and acid number of from 1-15 obtained from the reaction with the dicarboxylic acid anhydride.
  • copolymers preferably consist of copolymerised units of
  • the copolymers are preferably esterified up to an acid number of 0 to 10 with from 25-40% by weight of air-drying fatty acids.
  • Air-drying fatty acids are, for example, the fatty acids of linseed oil, soya bean oil, sunflower oil, cotton seed oil, groundnut oil, tall oil and safflower oil in their natural composition; that is to say, these natural air-drying fatty acids are mixtures of saturated, mono-unsaturated and/or poly-unsaturated fatty acids which have air-drying properties, the poly-unsaturated fatty acids mainly having isolated double bonds.
  • the fatty acids of the oils mentioned above have approximately the following compositions in percentages by weight:
  • the natural, drying fatty acids contain approximately 5-25% by weight of saturated C 8 -C 24 fatty acids, 20-60% by weight of monoolefinically unsaturated C 18 fatty acids, in particular oleic acid, and 20-75% by weight of tri-unsaturated and/or diunsaturated C 18 fatty acids containing mainly isolated double bonds.
  • drying fatty acids having several double bonds there may also be used polyunsaturated fatty acids with conjugated double bonds obtained by isomerisation, for example fatty acid mixtures containing 9, 11-linoleic acid.
  • the copolymers to be used for the esterification with the drying fatty acids and for the semi-ester formation with the dicarboxylic acid anhydride are prepared by known polymerisation processes, for example the process described in German Offenlegungsschrift No. 1,720,697. They contain the built-in monomers mainly in statistical distribution and they have average molecular weights (M n , number average) of approximately 2000 to 20,000, preferably from 3000 to 10,000, determined in xylene by the method of the lowering of the vapour pressure. Lower molecular weights impair the drying activity even in the presence of oximes and in particular also in the presence of anti-skinning agents.
  • M n average molecular weights
  • the new binder according to the invention it is advantageous to use a combination of certain molecular weights with certain acid numbers and possibly also a certain number of free acids containing groups which can be built into the molecule.
  • the final acid numbers of the binder are from 5 to 15.
  • the proportion of free acids should be characterised by the acid number of the first stage of the process, which is 0-10.
  • the dicarboxylic acid anhydrides which are added to the hydroxyl groups of the reaction products of glycidyl (meth)acrylate/polymer and drying fatty acids may be, for example, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, tetrahydrophthalic anhydride and its isomers or mixtures of these tetrahydrophthalic acid anhydrides, hexahydrophthalic acid anhydride, methyl hexahydrophthalic acid anhydride and endomethylene tetrahydrophthalic acid anhydride. Tetrahydrophthalic acid anhydrides are preferably used.
  • the drying fatty acids are used in quantities of from 22 to 50% by weight, based on the solid resin (copolymer + fatty acids + dicarboxylic acid anhydride), and are preferably used in quantities of from 25 to 40% by weight.
  • the addition of the dicarboxylic acid anhydrides, preferably tetrahydrophthalic acid anhydride or its isomers or mixtures of these anhydrides, to the hydroxyl groups of the resulting fatty acid-containing copolymers to form semi-esters is carried out at temperatures of about 50° C. to 180° C., preferably at 100° C. to 140° C.
  • the dicarboxylic acid anhydride is put into this reaction in such quantities that the acid number, based on the binder after semi-ester formation, is from 5 to 15, preferably from 6 to 12.
  • the quantity of dicarboxylic acid anhydride is from 0.5 to 3% by weight, always based on all the components of the binder (copolymer + fatty acids + dicarboxylic acid anhydride). Higher acid numbers severely retard drying in the presence of oximes.
  • the binders according to the invention are distinguished by excellent pigment absorption and wetting, little yellowing, rapid complete drying and good lacquer technical processing properties and the cured films obtained from them have a high gloss and good elasticity and hardness.
  • Their main advantage compared with the known art (see German Offenlegungsschrift No. 1,720,697), which enables them to be industrially utilised, lies in the fact that the properties mentioned above are preserved even after the addition of an anti-skinning agent, in the fact that no delay in drying occurs at room temperature and no skin is formed during storage of the lacquers, and in the fact that the freshly dried lacquers have less thermoplasticity.
  • the binders according to the invention are dissolved in known manner in organic solvents such as xylene, aromatic solvent mixtures and ethylene glycol acetate, with or without the addition of mineral spirits, and they may be processed as clear lacquers, but are preferably pigmented with the usual pigments and mixed with the usual quantities of auxiliary agents such as levelling agents, siccatives and the like.
  • the anti-skinning agents used may be aldoximes or ketoximes, for example butanone oxime, and they may be used in quantities of from 0.1 to 2.0% by weight, based on the solid binder.
  • novel binders according to the invention may be used as the only binders of a lacquer system although they may, of course, also be combined with other resins for the modification of properties, as is customary in the chemistry of lacquers.
  • binders according to the invention are binders according to the invention. These added substances produce an additional cross-linking effect through any hydroxyl groups present and increase the hardness and resistance of the lacquers as well as rendering the fresh lacquer coats more rapidly ready for use.
  • the lacquer films may be obtained by the usual methods of application, such as brush coating, spraying, dipping or application with doctor wipers and the like on the usual substrates such as metals, wood, paper, glass, ceramics, stone, concrete, plastics, etc. They are generally dried at from 15° C.-30° C. although both higher and lower drying temperatures may be employed.
  • the acid number is defined as mg KOH/g substance.
  • Example 1 of German Offenlegungsschrift No. 1,720,697 a solution of 120 g of styrene, 78 g of methyl methacrylate and 102 g of glycidyl methacrylate in 500 g of xylene is heated to 80° C. under nitrogen for 25 hours after the addition of 2.8 g of azodiisobutyronitrile as catalyst and 0.8 g of dodecylmercaptan as a regulator.
  • the conversion is said to be 100% and a clear, colourless polymer solution with an acid number of 1 and an outflow viscosity of 28 seconds from a DIN cup 4 at 20° C. is obtained.
  • the molecular weight M n determined osmometrically in xylene is approximately 2000.
  • This solution is stirred for 8 hours under nitrogen at 140° C. after the addition of 194 g of a commercial linoleic acid which has an acid number of 200.
  • the acid number of the solution obtained after this treatment is 5.
  • reaction solution is then stirred with 25 g of phthalic acid anhydride under nitrogen at 140° C. for 75 minutes.
  • the paste thereby obtained is mixed with 20 g of xylene, 3 g of ethylene glycol, 2 g of butanone oxime, 2 g of silicone oil (5% in xylene), 1.7 g of cobalt naphthenate (in the form of a solution in xylene with a metal content of 6% by weight) and 2.1 g of lead naphthenate (used as a solution in xylene with a metal content of 24% by weight), and the mixture is diluted to a spraying viscosity with xylene/turpentine oil (proportions by volume 8:2).
  • the diluted lacquer solutions obtained in this way are cast on glass plates and dried at room temperature while the plates are held vertically. Drying was found to be delayed by more than 10 hours. Pigment wetting is assessed as very good.
  • Determination of the pigment wetting is carried out with pigmented polymer solutions (50% by weight of titanium dioxide pigment, based on the solid resin) which have been adjusted to an outflow viscosity of 20 seconds from a DIN cup 4 at 20° C.
  • the diluted lacquer solutions are cast on glass plates and dried at room temperature with the plates and dried at room temperature with the plates held vertically.
  • the homogeneity of the film is assessed after drying. An assessment of very good pigment wetting means complete homogeneity while very poor pigment wetting means flocculation of the film (inhomogeneity).
  • Comparison Experiment 2 The product obtained in Comparison Experiment 2 was used to produce a lacquer by the same method as described in Comparison Experiment 1, using formulation A. Without the addition of an anti-skinning agent, the lacquer gelled within a short time.
  • the freshly prepared lacquer dried to a tack-free state within a few hours.
  • the lacquer was found to have lost its drying activity. It was then not free from tackiness even after a drying time of 5 hours.
  • This Example according to the invention demonstrates that a binder prepared from the same starting materials as those used in Comparison Experiment 1 and having the same composition but with the acid numbers defined according to the invention not only has excellent pigment wetting but also has a short drying time even after the addition of an anti-skinning agent.
  • Example 1 of German Offenlegungsschrift No. 1,720,697 192 parts of styrene, 124.8 parts of methyl methacrylate and 163.2 parts of glycidyl methacrylate are dissolved in 800 parts of xylene and the solution is polymerised to a conversion of 100% after the addition of 4.48 parts of azodiisobutyric acid nitrile (ADBN) and 1.28 parts of dodecylmercaptan as a regulator.
  • ADBN azodiisobutyric acid nitrile
  • Polymerisation is commenced at 80° C. and continued at 110° C. After three hours, a further 0.136 parts of ADBN are added. The temperature is then kept at 110° C. for 24 hours, and a further 0.136 parts of ADBN are added every 2 hours.
  • the colourless copolymer solution obtained has an outflow viscosity of 83 seconds (DIN 53 211), as compared with 28 seconds for Comparison Experiment 1.
  • 1159.0 parts of the copolymer solution are esterified with 306.0 parts of commercial linoleic acid at 140° C. to an acid number of 6, based on the solid substance.
  • reaction solution 600.0 parts of the clear, pale yellow reaction solution are then converted to the semi-ester by reaction with 3.2 parts of phthalic acid anhydride at 120° C. in the course of 45 minutes.
  • the solvent-free semi-ester has an acid number of 13.
  • the viscosity of the reaction solution is 5925 cp (at 20° C.).
  • the molecular weight Mn of the semi-ester is approximately 3000, determined osmometrically in xylene.
  • a white lacquer is prepared from the pale yellow solution of the semi-ester, using lacquer formulation A.
  • the lacquer can be preserved with an anti-skinning agent.
  • Freshly prepared lacquers have drying times of 2 hours.
  • a lacquer which has been stored for three days is found to have preserved its drying activity and has a drying time of 2 hours. Pigment wetting is assessed as very good.
  • Lacquer formulation A mentioned above contains lead naphthenate as a siccative, among others. In the binders mentioned above, this siccative tends to cause turbidity in the lacquer solution. It is therefore in many cases advisable to prepare lead-free lacquers in accordance with the following lacquer formulation B:
  • zirconium-containing lacquers obtained from the samples of the Comparison Experiment are found to have an unpleasant thermoplastic quality which can be assessed by touching the surface of the lacquer with a finger or the palm of the hand. Under this test, higher thermoplastic lacquers are found to stick.
  • the low thermoplasticity of the freshly dried lacquers is another technical advantage which is particularly important for motor car body repair work since freshly lacquered cars are quite likely to be strongly heated by exposure to the sun.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
US05/876,539 1977-02-12 1978-02-09 Air-drying acrylate lacquer binders Expired - Lifetime US4146519A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772706106 DE2706106A1 (de) 1977-02-12 1977-02-12 Lufttrocknende acrylat-lackbindemittel
DE2706106 1977-02-12

Publications (1)

Publication Number Publication Date
US4146519A true US4146519A (en) 1979-03-27

Family

ID=6001096

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/876,539 Expired - Lifetime US4146519A (en) 1977-02-12 1978-02-09 Air-drying acrylate lacquer binders

Country Status (11)

Country Link
US (1) US4146519A (de)
JP (1) JPS5399231A (de)
AT (1) AT358686B (de)
BE (1) BE863849A (de)
DE (1) DE2706106A1 (de)
ES (1) ES466866A1 (de)
FR (1) FR2380330A1 (de)
GB (1) GB1581425A (de)
IT (1) IT1102386B (de)
NL (1) NL7801577A (de)
SE (1) SE7801580L (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4242243A (en) * 1979-07-18 1980-12-30 E. I. Du Pont De Nemours And Company High solids ambient temperature curing coatings of acrylic-fatty acid drying oil resins
US4253397A (en) * 1979-10-24 1981-03-03 Rohm And Haas Company Method of printing with lithographic ink of reduced volatile solvent content for reducing atmospheric pollution
US4255196A (en) * 1979-02-23 1981-03-10 Rohm And Haas Company Lithographic ink of reduced volatile solvent content for reducing atmospheric pollution
US4267082A (en) * 1978-05-03 1981-05-12 Bayer Aktiengesellschaft Air-cross-linkable polyacrylate lacquer binders containing chemically fixed wood preservatives
US4303565A (en) * 1980-08-29 1981-12-01 Mobil Oil Corporation Composition comprising ester of epoxy, unsaturated fatty acid dimer or trimer and acid containing addition polymer, and aqueous coating compositions prepared therefrom
US4309321A (en) * 1979-08-17 1982-01-05 Kansai Paint Co., Ltd. Aqueous coating composition
USRE31309E (en) * 1979-07-18 1983-07-12 E. I. Du Pont De Nemours And Company High solids ambient temperature curing coatings of acrylic-fatty acid drying oil resins
US4400489A (en) * 1980-11-27 1983-08-23 Bayer Aktiengesellschaft Aerially-crosslinking polyacrylate coating agents
US4981944A (en) * 1988-06-15 1991-01-01 Akzo N. V. Liquid coating composition curable at ambient temperatures
EP0408858A1 (de) * 1989-05-19 1991-01-23 BASF Corporation Copolymere zur Verwendung für Beschichtungen mit gering flüchtigen organischen Anteilen und hohen Feststoffgehalten
EP1197325A3 (de) * 2000-10-11 2002-09-04 Andreas Peter Galac Verfahren zur Herstellung von Verbundglas mit einer Mattierung
CN112812013A (zh) * 2020-12-30 2021-05-18 安徽熙泰智能科技有限公司 一种用于引线键合保护胶的化合物及其制备方法和快干型引线键合保护胶

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2934950A1 (de) * 1979-08-29 1981-03-19 Bayer Ag, 5090 Leverkusen Lufttrocknende, fettsaeuremodifizierte lackbindemittel auf der grundlage von fumar- bzw. maleinsaeurebisglycidylestercopolymerisaten
DE3347630A1 (de) * 1982-12-30 1984-08-02 Nippon Paint Co., Ltd., Osaka Harzmassen, verfahren zu ihrer herstellung und sie enthaltende beschichtungsmassen

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB767476A (en) * 1954-03-19 1957-02-06 Canadian Ind 1954 Ltd Styrene copolymers
CA551429A (en) * 1958-01-07 Du Pont Company Of Canada Limited Vinyl-type copolymer-containing coating composition
GB793776A (en) * 1954-04-07 1958-04-23 Ici Ltd Esters of drying oil acids with certain vinyl polymers
GB858827A (en) * 1958-03-27 1961-01-18 Bataafsche Petroleum Improvements in or relating to the production of an alkyd resin from an epoxy resin
GB1227398A (de) * 1967-08-16 1971-04-07
GB1399159A (en) * 1971-10-05 1975-06-25 Vianova Kunstharz Ag Resins

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA551429A (en) * 1958-01-07 Du Pont Company Of Canada Limited Vinyl-type copolymer-containing coating composition
GB767476A (en) * 1954-03-19 1957-02-06 Canadian Ind 1954 Ltd Styrene copolymers
GB793776A (en) * 1954-04-07 1958-04-23 Ici Ltd Esters of drying oil acids with certain vinyl polymers
GB858827A (en) * 1958-03-27 1961-01-18 Bataafsche Petroleum Improvements in or relating to the production of an alkyd resin from an epoxy resin
GB1227398A (de) * 1967-08-16 1971-04-07
GB1399159A (en) * 1971-10-05 1975-06-25 Vianova Kunstharz Ag Resins

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267082A (en) * 1978-05-03 1981-05-12 Bayer Aktiengesellschaft Air-cross-linkable polyacrylate lacquer binders containing chemically fixed wood preservatives
US4255196A (en) * 1979-02-23 1981-03-10 Rohm And Haas Company Lithographic ink of reduced volatile solvent content for reducing atmospheric pollution
US4242243A (en) * 1979-07-18 1980-12-30 E. I. Du Pont De Nemours And Company High solids ambient temperature curing coatings of acrylic-fatty acid drying oil resins
USRE31309E (en) * 1979-07-18 1983-07-12 E. I. Du Pont De Nemours And Company High solids ambient temperature curing coatings of acrylic-fatty acid drying oil resins
US4309321A (en) * 1979-08-17 1982-01-05 Kansai Paint Co., Ltd. Aqueous coating composition
US4253397A (en) * 1979-10-24 1981-03-03 Rohm And Haas Company Method of printing with lithographic ink of reduced volatile solvent content for reducing atmospheric pollution
US4303565A (en) * 1980-08-29 1981-12-01 Mobil Oil Corporation Composition comprising ester of epoxy, unsaturated fatty acid dimer or trimer and acid containing addition polymer, and aqueous coating compositions prepared therefrom
US4400489A (en) * 1980-11-27 1983-08-23 Bayer Aktiengesellschaft Aerially-crosslinking polyacrylate coating agents
US4981944A (en) * 1988-06-15 1991-01-01 Akzo N. V. Liquid coating composition curable at ambient temperatures
EP0408858A1 (de) * 1989-05-19 1991-01-23 BASF Corporation Copolymere zur Verwendung für Beschichtungen mit gering flüchtigen organischen Anteilen und hohen Feststoffgehalten
EP1197325A3 (de) * 2000-10-11 2002-09-04 Andreas Peter Galac Verfahren zur Herstellung von Verbundglas mit einer Mattierung
CN112812013A (zh) * 2020-12-30 2021-05-18 安徽熙泰智能科技有限公司 一种用于引线键合保护胶的化合物及其制备方法和快干型引线键合保护胶

Also Published As

Publication number Publication date
FR2380330A1 (fr) 1978-09-08
ES466866A1 (es) 1978-10-01
IT7848005A0 (it) 1978-02-10
BE863849A (fr) 1978-08-10
ATA93978A (de) 1980-02-15
SE7801580L (sv) 1978-08-13
DE2706106A1 (de) 1978-08-17
JPS5399231A (en) 1978-08-30
GB1581425A (en) 1980-12-10
NL7801577A (nl) 1978-08-15
AT358686B (de) 1980-09-25
IT1102386B (it) 1985-10-07

Similar Documents

Publication Publication Date Title
US4146519A (en) Air-drying acrylate lacquer binders
CA1190339A (en) Aqueous, oxidatively drying coating composition
US4010126A (en) Aqueous emulsion copolymers of vinyl alkanoates, alkyl, acrylates, and acrylic modified alkyds
AU2016254105B2 (en) Aqueous dispersions
US4591518A (en) Acrylic functional urethane alkyd resin coating compositions
JPH0261513B2 (de)
WO1991009888A1 (de) Lösliche vernetzbare copolymerisate auf der basis von vinylester-, vinylaromat- und acrylatmonomeren, verfahren zu ihrer herstellung sowie ihre verwendung in beschichtungsmitteln
US3166524A (en) Polymer systems and method of preparation thereof
US7138465B2 (en) Polymer-modified resins
DE2827592A1 (de) Bindemittel fuer ueberzugsmassen
US4129537A (en) Air-drying acrylate lacquer binders
JPH09512566A (ja) 水で希釈できる自然乾燥塗料結合剤の製造方法およびその使用
GB1599045A (en) Coating compositions
US3258438A (en) Addition polymer compositions and methods of producing them
US3306866A (en) Stable emulsion of copolymerized alkyd resins and addition polymerizable monomers
JPH01138216A (ja) 水性グラフト共重合体エマルジョン、その製造法および水希釈可能な自然乾燥塗料のための結合剤としてのエマルジョンの使用
US4186116A (en) Air-drying and oven-drying acrylate lacquer binders
US4304695A (en) Air-drying, fatty acid-modified lacquer binders, based on fumaric or maleic acid bis-glycidyl ester copolymers
GB2170810A (en) Coating compositions
US4133785A (en) Process for preparing a film-forming material
JPH06329984A (ja) 物理的迅速乾燥結合剤混合物および木材支持体を塗布するためのそれらの使用
RU2711366C2 (ru) Композиция для получения алкидных смол
US4450251A (en) Thermosetting aqueous varnish compositions
JPS6258374B2 (de)
JPS6239623B2 (de)